Nanocrystals (NCs) discussed in this Review are tiny crystals of metals, semiconductors, and magnetic material consisting of hundreds to a few thousand atoms each. Their size ranges from 2-3 to about 20 nm. What is special about this size regime that placed NCs among the hottest research topics of the last decades? The quantum mechanical coupling * To whom correspondence should be addressed. E-mail: dvtalapin@uchicago.edu. † The University of Chicago. ‡ Argonne National Lab. Chem. Rev. 2010, 110, 389–458 389

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Prospects of Colloidal Nanocrystals for Electronic and Optoelectronic Applications

Covalent organic frameworks (COFs) represent an exciting new type of porous organic materials, which are ingeniously constructed with organic building units via strong covalent bonds. The well-defined crystalline porous structures together with tailored functionalities have offered the COF materials superior potential in diverse applications, such as gas storage, adsorption, optoelectricity, and catalysis. Since the seminal work of Yaghi and co-workers in 2005, the rapid development in this research area has attracted intensive interest from researchers with diverse expertise. This critical review describes the state-of-the-art development in the design, synthesis, characterisation, and application of the crystalline porous COF materials. Our own opinions on further development of the COF materials are also presented for discussion (155 references).

Covalent organic frameworks (COFs): from design to applications

The isolation of graphene in 2004 from graphite was a defining moment for the “birth” of a field: two-dimensional (2D) materials In recent years, there has been a rapidly increasing number of papers focusing on non-graphene layered materials, including transition-metal dichalcogenides (TMDs), because of the new properties and applications that emerge upon 2D confinement Here, we review significant recent advances and important new developments in 2D materials “beyond graphene” We provide insight into the theoretical modeling and understanding of the van der Waals (vdW) forces that hold together the 2D layers in bulk solids, as well as their excitonic properties and growth morphologies Additionally, we highlight recent breakthroughs in TMD synthesis and characterization and discuss the newest families of 2D materials, including monoelement 2D materials (ie, silicene, phosphorene, etc) and transition metal carbide- and carbon nitride-based MXenes We then discuss the doping and functionalization of 2

Recent Advances in Two-Dimensional Materials beyond Graphene

Advanced energy conversion and storage (ECS) devices (including fuel cells, photoelectrochemical water splitting cells, solar cells, Li-ion batteries and supercapacitors) are expected to play a major role in the development of sustainable technologies that alleviate the energy and environmental challenges we are currently facing. The successful utilization of ECS devices depends critically on synthesizing new nanomaterials with merits of low cost, high efficiency, and outstanding properties. Recent progress has demonstrated that nanostructured metal chalcogenides (MCs) are very promising candidates for efficient ECS systems based on their unique physical and chemical properties, such as conductivity, mechanical and thermal stability and cyclability. In this review, we aim to provide a summary on the liquid-phase synthesis, modifications, and energy-related applications of nanostructured metal chalcogenide (MC) materials. The liquid-phase syntheses of various MC nanomaterials are primarily categorized with the preparation method (mainly 15 kinds of methods). To obtain optimized, enhanced or even new properties, the nanostructured MC materials can be modified by other functional nanomaterials such as carbon-based materials, noble metals, metal oxides, or MCs themselves. Thus, this review will then be focused on the recent strategies used to realize the modifications of MC nanomaterials. After that, the ECS applications of the MC/modified-MC nanomaterials have been systematically summarized based on a great number of successful cases. Moreover, remarks on the challenges and perspectives for future MC research are proposed (403 references).

Nanostructured metal chalcogenides: synthesis, modification, and applications in energy conversion and storage devices

The performance of electronic and optoelectronic devices based on two-dimensional layered crystals, including graphene, semiconductors of the transition metal dichalcogenide family such as molybdenum disulphide (MoS2) and tungsten diselenide (WSe2), as well as other emerging two-dimensional semiconductors such as atomically thin black phosphorus, is significantly affected by the electrical contacts that connect these materials with external circuitry. Here, we present a comprehensive treatment of the physics of such interfaces at the contact region and discuss recent progress towards realizing optimal contacts for two-dimensional materials. We also discuss the requirements that must be fulfilled to realize efficient spin injection in transition metal dichalcogenides.

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Electrical contacts to two-dimensional semiconductors

The tremendous interest in nanoscale structures such as quantum dots (zero-dimension) and wires (quasi-one-dimension) stems from their size-dependent properties. One-dimensional (1D) semiconductor nanostructures are of particular interest because of their potential applications in nanoscale electronic and optoelectronic devices. For 1D semiconductor nanomaterials to have wide practical application, however, several areas require further development. In particular, the fabrication of desired 1D nanomaterials with tailored atomic structures and their assembly into functional devices are still major challenges for nanotechnologists. In this review, we focus on the status of research on the formation of nanowire structures via highly anisotropic growth of nanocrystals of semiconductor and metal oxide materials with an emphasis on the structural characterization of the nucleation, initial growth, defects and interface structures, as well as on theoretical analyses of nanocrystal formation, reactivity and stability. We review various methods used and mechanisms involved to generate 1D nanostructures from different material systems through self-organized growth techniques including vapor–liquid–solid growth, oxide-assisted chemical vapor deposition (without a metal catalyst), laser ablation, thermal evaporation, metal-catalyzed molecular beam epitaxy, chemical beam epitaxy and hydrothermal reaction. 1D nanostructures grown by these technologies have been observed to exhibit unusual growth phenomena and unexpected properties, e.g., diameter-dependent and temperature-dependent growth directions, structural transformation by enhanced photothermal effects and phase transformation induced by the point contact reaction in ultra-thin semiconductor nanowires. Recent progress in controlling growth directions, defects, interface structures, structural transformation, contacts and hetero-junctions in 1D nanostructures is addressed. Also reviewed are the quantitative explorations and predictions of some challenging 1D nanostructures and descriptions of the growth mechanisms of 1D nanostructures, based on the energetic, dynamic and kinetic behaviors of the building block nanostructures and their surfaces and/or interfaces.

Growth of nanowires

The metal-insulator transition is one of the remarkable electrical properties of atomically thin molybdenum disulphide. Although the theory of electron-electron interactions has been used in modelling the metal-insulator transition in molybdenum disulphide, the underlying mechanism and detailed transition process still remain largely unexplored. Here we demonstrate that the vertical metal-insulator-semiconductor heterostructures built from atomically thin molybdenum disulphide are ideal capacitor structures for probing the electron states. The vertical configuration offers the added advantage of eliminating the influence of large impedance at the band tails and allows the observation of fully excited electron states near the surface of molybdenum disulphide over a wide excitation frequency and temperature range. By combining capacitance and transport measurements, we have observed a percolation-type metal-insulator transition, driven by density inhomogeneities of electron states, in monolayer and multilayer molybdenum disulphide. In addition, the valence band of thin molybdenum disulphide layers and their intrinsic properties are accessed.

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Probing the electron states and metal-insulator transition mechanisms in molybdenum disulphide vertical heterostructures

We report the observation of a dense triangular network of one-dimensional (1D) metallic modes in a continuous and uniform monolayer of MoSe(2) grown by molecular-beam epitaxy. High-resolution transmission electron microscopy and scanning tunneling microscopy and spectroscopy studies show that these 1D modes are midgap states at inversion domain boundaries. Scanning tunneling microscopy and spectroscopy measurements further reveal intensity undulations of the metallic modes, presumably arising from the superlattice potentials due to the moire pattern and the quantum confinement effect. A dense network of the metallic modes with a high density of states is of great potential for heterocatalysis applications. The interconnection of such midgap 1D conducting channels may also imply new transport behaviors distinct from the 2D bulk.

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Dense network of one-dimensional midgap metallic modes in monolayer MoSe2 and their spatial undulations.

The Size-dependent growth direction of ZnSe nanowires

Tetrapod-shaped CdSe nanocrystals have been successfully synthesized in high yields using a simple method of controlling the protonic acidity of the reaction system. A possible growth mechanism is discussed on the basis of the surface modification of H+ present. The crystal structure of CdSe tetrapods is determined by high-resolution transmission electron microscopy analysis to have a zinc blende core at the center with four wurtzite arms growing out from the core along four [111] directions. The electronic structure of CdSe tetrapods is studied theoretically in comparison with that of spherical dots.

Yuan Cai

Papers

Growth of nanowires

Probing the electron states and metal-insulator transition mechanisms in molybdenum disulphide vertical heterostructures

Dense network of one-dimensional midgap metallic modes in monolayer MoSe2 and their spatial undulations.

The Size-dependent growth direction of ZnSe nanowires

CdSe Nano-tetrapods: Controllable Synthesis, Structure Analysis, and Electronic and Optical Properties